Ether compounds and their use

ABSTRACT

There are disclosed novel ether compounds of the general formula: ##STR1## wherein R 1 , R 2  and R 3  are each hydrogen or the like; A is a group of the general formula: ##STR2## B is a group of the general formula: ##STR3## and X is oxygen or sulfur; and harmful-organism controlling agents containing them as active ingredients.

This application has been filed under USC 371 as a National stageapplication of PCT/JP95/00763 filed Apr. 19, 1995.

TECHNICAL FIELD

The present invention relates to ether compounds and their use. Moreparticularly, the present invention relates to ether compounds whichhave excellent controlling effects against harmful organisms and toharmful-organism controlling agents containing them as activeingredients.

DISCLOSURE OF THE INVENTION

The present inventors have intensively studied to find compounds whichhave excellent controlling effects against harmful organisms. As aresult, they have found that ether compounds of the general formula P-1as depicted below have excellent controlling effects against harmfulorganisms, thereby completing the present invention.

Thus the present invention provides ether compounds (hereinafterreferred to as the present compound(s)) of the general formula: ##STR4##wherein R¹ is hydrogen or chlorine; R² and R³ are independently hydrogenor methyl;

A is a group of the general formula: ##STR5## wherein R⁴ is hydrogen,chlorine or methyl; and R⁵ and R⁶ are independently hydrogen orchlorine;

B is a group of the general formula: ##STR6## wherein R⁷ and R⁸ areindependently hydrogen or fluorine; and X is oxygen or sulfur; andharmful-organism controlling agents containing them as activeingredients.

EMBODIMENTS FOR MAKING THE INVENTION

In the present compounds, it is preferred from the viewpoint ofharmful-organism controlling activity that A is a group of the generalformula: ##STR7## wherein R⁴ is as defined above. Among them, a groupwherein R⁴ is hydrogen is preferred, and R¹ is preferably hydrogen.

The present compounds can be produced, for example, by the followingprocesses.

(Production process a)

This is a production process in which a phenol derivative of the generalformula: ##STR8## wherein R¹ and A are as defined above, with a compoundof the general formula: ##STR9## wherein R², R³, B and X are as definedabove; and L is halogen (e.g., chlorine, bromine, iodine), mesyloxy ortosyloxy.

(Production process b)

This is a production process in which a compound of the general formula:##STR10## wherein R¹, R², R³, A and X are as defined above, or an alkalimetal salt thereof (e.g., lithium salt, sodium salt, potassium salt), isreacted with a compound of the general formula:

    L--B                                                       (P-6)

wherein B and L are as defined above.

(Production process c)

This is a production process in which a compound of the general formula:##STR11## wherein R¹, R², R³, A and L are as defined above, is reactedwith a compound of the general formula:

    H--X--B                                                    (P-8)

wherein B and X are as defined above, or an alkali metal salt thereof(e.g., lithium salt, sodium salt, potassium salt).

In the production processes a, b and c, the reaction is preferablyeffected in the presence of a base without any solvent or in an inertorganic solvent (however, when an alkali metal salt of the compound ofthe general formula P-5 or P-8 is used for the reaction in theproduction process b and c, there is no need to use a base).

This reaction is usually effected in an inert organic solvent. As thesolvent which can be used, there can be mentioned, for example, aromatichydrocarbons such as benzene, toluene, xylene and chlorobenzene;nitriles such as acetonitrile, propionitrile and isobutyronitrile;ketones such as acetone, methyl isobutyl ketone and methyl ethyl ketone;methanol, ethanol, n-propyl alcohol and the like; ethers such asmethoxyethane, tetrahydrofuran and dioxane; polar solvents such asN,N-dimethylformamide, N,N-di-methylacetamide, dimethylsulfoxide,sulforane and hexamethylphosphoric triamide; water; or mixtures thereof.To make more smooth progress in the reaction, phase transfer catalystsmay be added, such as benzyltriethylammonium chloride andtetra-n-butylammonium bromide.

As the base which can be used, there can be mentioned, for example,alkali metals such as sodium and potassium; alkali metal hydroxides suchas sodium hydroxide and potassium hydroxide; alkali metal carbonatessuch as sodium carbonate and potassium carbonate; alkali metal hydridessuch as sodium hydride; metal alkoxides such as sodium ethoxide andsodium methoxide; and organic bases such as pyridine, triethyl-amine,N,N-dimethylaniline and 4-N,N-dimethylaminopyridine.

In the production processes, a, b and c, although the reactiontemperature is not particularly limited, the reaction is usuallyeffected in the range of -30° C. to 200° C. or the boiling point of thesolvent used, preferably in the range of 20° C. to 110° C. The reactiontime is usually 0.5 to 24 hours.

The molar ratio of the phenol derivative of the general formula P-3 tothe compound of the general formula P-4, which are used in theproduction process a, is usually 1:0.5 to 2, preferably 1:0.7 to 1.5.The molar ratio of the compound of the general formula P-5 to thecompound of the general formula P-6, which are used in the productionprocess b, is usually 1:0.5 to 10, preferably 1:0.8 to 2. The molarratio of the compound of the general formula P-7 to the compound of thegeneral formula P-8, which are used in the production process c, isusually 1:1 to 10, preferably 1:1.1 to 1.5.

In the production processes a, b and c, after completion of thereaction, the reaction mixture is subjected to ordinary post-treatmentssuch as extraction with an organic solvent and concentration. Thus thepresent compounds can be isolated. If necessary, purification may becarried out by recrystallization, column chromatography or the like.

Typical examples of the present compounds are shown below.

Compounds of the general formulas: ##STR12## wherein R¹, R², R³ and Xare as defined in Table 1; and

                  TABLE 1    ______________________________________    R.sup.1          R.sup.2  R.sup.3                          X     R.sup.1                                    R.sup.2                                           R.sup.3                                                X    ______________________________________    H     H        H      O     H   H      H    S    Cl    H        H      O     Cl  H      H    S    H     H        CH.sub.3                          O     H   H      CH.sub.3                                                S    H     CH.sub.3 H      O     H   CH.sub.3                                           H    S    H     CH.sub.3 CH.sub.3                          O     H   CH.sub.3                                           CH.sub.3                                                S    Cl    H        CH.sub.3                          O     Cl  H      CH.sub.3                                                S    Cl    CH.sub.3 H      O     Cl  CH.sub.3                                           H    S    Cl    CH.sub.3 CH.sub.3                          O     Cl  CH.sub.3                                           CH.sub.3                                                S    ______________________________________

those of the general formulas: ##STR13## wherein R¹, R²,R³ and X are asdefined in Table 2.

                  TABLE 2    ______________________________________    R.sup.1          R.sup.2  R.sup.3                          X     R.sup.1                                    R.sup.2                                           R.sup.3                                                X    ______________________________________    H     H        H      O     H   H      H    S    Cl    H        H      O     Cl  H      H    S    H     H        CH.sub.3                          O     H   H      CH.sub.3                                                S    H     CH.sub.3 H      O     H   CH.sub.3                                           H    S    Cl    H        CH.sub.3                          O     Cl  H      CH.sub.3                                                S    Cl    CH.sub.3 H      O     Cl  CH.sub.3                                           H    S    ______________________________________

The compounds of the general formulas P-4, P-6 and P-8, which areintermediates for use in the production of the present compounds, may beobtained from commercial sources; however, the compounds of the generalformula P-4 can be produced, for example, according to the methoddescribed in Synthesis, 573 (1980), or the compounds of the generalformula P-8 can be produced, for example, according to the methoddescribed in the publication JP-A 56-90059.

The compounds of the general formulas P-5 and P-7 can be produced, forexample, from the compounds of the general formula P-3 through thefollowing reaction scheme: ##STR14## wherein R¹, R², R³, A and L are asdefined above; L' is halogen (e.g., chlorine, bromine, iodine); and R⁹is C₁ -C₄ alkyl (e.g., methyl, ethyl).

The phenol derivatives of the general formula P-3 can be produced, forexample, by the following process.

This is a process in which a phenol ester derivative of the generalformula: ##STR15## wherein R¹ and A are as defined above and R⁹ is C₁-C₄ alkyl (e.g., methyl, ethyl) or phenyl, is hydrolyzed under the basicconditions.

As the base which can be used, there can be mentioned, for example,alkali metal hydroxides such as sodium hydroxide and potassiumhydroxide; alkaline earth metal hydroxides such as ballium hydroxide;alkali metal carbonates such as potassium carbonate and sodiumcarbonate.

This reaction is usually effected in a solvent. As the solvent which canbe used, there can be mentioned, for example, alcohols such as methanol,ethanol, n-propyl alcohol, ethylene glycol and diethylene glycol; water;or mixtures thereof.

The reaction is usually effected in the range of 0° to 200° C. or theboiling point of the solvent used, preferably in the range of 20° to120° C. The reaction time is usually 1 to 500 hours.

As the amounts of reagents to be used in the reaction, the base can beused at any mole to 1 mole of the phenol derivative of the generalformula P-9, preferably at a ratio of 1 to 2 moles.

The phenol ester derivatives of the general formula P-9 can be produced,for example, by the following process.

This is a process in which a phenol ester compound of the generalformula: ##STR16## wherein R¹, R⁹ and L are as defined above, is reactedwith a compound of the general formula:

    A--H                                                       (P-11)

wherein A is as defined above, in the presence of a base.

This reaction is usually effected in an inert organic solvent. As thesolvent which can be used, there can be mentioned, for example, aromatichydrocarbons such as benzene, toluene, xylene and chlorobenzene;nitriles such as acetonitrile, propionitrile and isobutyronitrile;ketones such as acetone, methyl isobutyl ketone and methyl ethyl ketone;alcohols such as methanol, ethanol and n-propyl alcohol; ethers such asdiethyl ether, diisopropyl ether, 1,2-dimethoxyethane, tetrahydrofuranand dioxane; polar solvents such as N,N-dimethylformamide,N,N-dimethylacetamide, dimethylsulfoxide, sulforane andhexamethylphosphoric triamide; or mixtures thereof.

As the base which can be used, there can be mentioned, for example,alkali metals such as sodium and potassium; alkali metal hydroxides suchas sodium hydroxide and potassium hydroxide; alkali metal carbonatessuch as sodium carbonate and potassium carbonate; alkali metal hydridessuch as sodium hydride; alkali metal alkoxides (e.g., C₁ -C₄ alkoxidessuch as methoxides and ethoxides) such as sodium ethoxide and sodiummethoxide; and organic bases such as pyridine, triethylamine,N,N-dimethylaniline and 4-N,N-dimethylaminopyridine.

The reaction is usually effected in the range of 0° to 200° C. or theboiling point of the solvent used, preferably in the range of 20° to120° C. The reaction time is usually 1 to 50 hours.

The amounts of reagents to be used in the reaction are usually in theratio of 1 to 10 moles, preferably 1 to 2 moles, for each of thecompound of the general formula P-11 and the base, to 1 mole of thephenol ester compound of the general formula P-10.

The present compounds exhibit excellent controlling effects againstharmful organisms, for example, noxious insects and noxious ticks andmites, such as described below:

Noxious insects of Hemiptera

planthoppers (Delphacidae) such as brown rice planthopper (Nilaparvatalugens), white-backed rice planthopper (Sogatella furcifera) and smallbrown planthopper (Laodelphax striatellus); leafhoppers(Deltocephalidae) such as green rice leafhopper (Nephotettixcincticeps), green rice leafhopper (Nephotettix virescens), green riceleafhopper (Nephotettix nigropictus), zig-zag rice leafhopper (Reciliadorsalis), tea green leafhopper (Empoasca onukii) and grape leafhopper(Arboridia apicalis); aphids (Aphididae) such as cotton aphid (Aphisgossypii) and green peach aphid (Myzus persicae); stink bugs(Pentatomidae); whiteflies (Aleyrodidae) such as sweetpotato whitefly(Bemisia tabaci) and greenhouse whitefly (Trialeurodes vaporariorum);scale insects (Coccidae); lace bugs (Tingidae); psyllids (Psyllidae),etc.

Noxious insects of Lepidoptera

pyralid moths (Pyralidae) such as rice stem borer (Chilo suppressalis),rice leafroller (Cnaphalocrocis medinalis) and Indian meal moth (Plodiainterpunctella); owlet moths (Noctuidae) such as common cutworm(Spodoptera litura), rice armyworm (Spodoptera exigua) and cabbagearmyworm (Mamestra brassicae); white and sulfer butterflies (Pieridae)such as common cabbageworm (Pieris rapae crucivora); tortricid moths(Tortricidae) such as Adoxophyes spp.; Carposinidae; lionetiid moths(Lyonetiidae); leafblotch miners (Gracillariidae); gelechiid moths(Gelechiidae); tussock moths (Lymantriidae); Plusiae; Agrotis spp. suchas cutworm (Agrotis segetum) and black cutworm (Agrotis ipsilon);Heliothis spp.; diamondback moth or cabbage moth (Plutella xylostella);casemaking clothes moth or case-bearing dothes moth (Tinea pellionella);webbing clothes moth or common clothes moth (Tineola bisselliella), etc.

Noxious insects of Diptera

mosquitos (Calicidae) such as common mosquito (Culex pipiens pallens)and Cules tritaeniorhynchus; Aedes spp. such as Aedes aegypti and Aedesalbopictus; Anopheles spp. such as Anophelinae sinensis; midges(Chironomidae); house flies (Muscidae) such as house fly (Muscadomestica) and false stablefly (Muscina stabulans); Calliphoridae;Sarcophagidae; anthomyild flies (Anthomyiidae) such as lesser housefly(Fannia canicularis), seedcorn maggot (Hylemya platura) and onion maggot(Hylemya antique); gall midges (Cecidomyiidae); fruit flies(Tephritidae); shore flies (Ephydridae); small fruit flies(Drosophilidae); moth flies (Psychodidae); black flies (Simuliidae);Tabanidae; stable flies (Stomoxyidae), etc.

Noxious insects of Coleoptera

corn rootworms such as western corn rootworm (Diabrotica virgifera) andsouthern corn rootworm (Diabrotica undecimpunctata); scarabs(Scarabaeidae) such as cupreous chafer (Anomala cuprea) and soybeanbeetle (Anomala rufocuprea); weevils (Curculionidae) such as maizeweevil (Sitophilus zeamais), rice water weevil (Lissor-phoptrusoryzophilus) and azuki bean weevil (Calosobruchys chinensis); darklingbeetles (Tenebrionidae) such as yellow mealworm (Tenebrio molitor) andred flour beetle (Tribolium castaneum); lef beetles (Chrysomelidae) suchas striped flea beetle (Phyllotreta striolata) and cucurbit leaf beetle(Aulacophora femoralis); drugstore beetles (Anobiidae); Epilachna spp.such as twenty-eight-spotted ladybird (Epilachna vigintiocto punctata);powder post beetles (Lyctidae); false powderpost beetles (Bostrychidae);longhorn beetles (Cerambycidae), etc.

Noxious insects of Dictyoptera

German cockroach (Blattella germanica), smokybrown cockroach(Periplaneta fuliginosa), American cockroach (Peroplaneta americana),brown cockroach (Peri planeta brunnea), oriental cockroach (Blattaorientalis), etc.

Noxius insects of Thysanoptera

Thrips palmi, yellow tea thrips (Scirtothrips dorsalis), flower thrips(Thrips hawaiiensis), etc.

Noxious insects of Hymenoptera

ants (Formicidae); sawflies (Tenthredinidae) such as cabbage sawfly(Athalia rosae japonensis), etc.

Noxious insects of Orthoptera

mole crickets (Gryllotalpidae), grasshoppers (Acrididae), etc.

Noxious insects of Aphaniptera

Purex irritans etc.

Noxious insects of Anoplura

Pediculus humanus capitis, Phthirus pubis, etc.

Noxious insects of Isoptera

Reticulitermes speratus, Formosan subterranean termite (Coptotermesformosanus), etc.

Spider mites (Tetranychidae)

carmine spider mite (Tetranychus cinnabarinus), two-spotted spider mite(Tetranychus urticae), Kanzawa spider mite (Tetranychus kazawai), citrusred mite (Panonychus citri), fruit tree red spider mite (Panonychusulmi), etc.

Ticks (Ixodidae)

Boophilus microphus etc.

House dust mites

Grain mites, Dermatophagoides, Cheyletid mites, Ornitonyssus, etc.

If the present compounds are used in combination with other insecticidesand/or acaricides, the controlling effects achieved by the presentcompounds can find practical applications to more various places for useagainst a wider variety of noxious insects.

As the insecticide and/or acaricide, which are suitable for combineduse, there can be mentioned, for example, organophosphorus compoundssuch as Fenitrothion O,O-dimethylO-(3-methyl-4-nitrophenyl)phosphorothioate!, Fenthion O,O-dimethylO-(3-methyl-4-(methylthio)phenyl!phosphorothioate!, DiazinonO,O-diethyl-O-2-isopropyl-6-methylpyrimidin-4-ylphosphorothioate!,Chlorpyriphos O,O-diethyl-O-3,5,6-trichloro-2-pyridylphosphorothioate!,Acephate O,S-dimethylacetylphosphoramidothio-ate!, MethidathionS-2,3-dihydro-5-methoxy-2-oxo-1,3,4-thiadiazol-3-ylmethylO,O-di-methylphosphorodithioate!, Ethylthiometon O,O-diethylS-2-ethylthioethylphosphorodithioate!, DDVP2,2-dichlorovinyldimethylphosphate!, Sulprofos O-ethylO-4-(methyl-thio)phenyl S-propylphosphorodithioate!, CyanophosO-4-cyanophenyl O,O-dimethyl-phosphorothioate!, Salithion2-methoxy-4H-1,3,2-benzodioxaphosphinine-2-sulfide!, DimethoateO,O-dimethyl-S-(N-methylcarbamoylmethyl)dithiophosphate!, Phenthoateethyl 2-dimethoxyphosphinothioylthio(phenyl)acetate!, Malathiondiethyl(dimethoxy-phosphinothioylthio)succinate!, Trichlorfon dimethyl2,2,2-trichloro-1-hydroxyethyl-phosphonate!, Azinphos-methylS-3,4-dihydro-4-oxy-1,2,3-benzotriazin-3-ylmethylO,O-dimethylphosphorodithioate! and Monocrotophos dimethyl(E)-1-methyl-2-(methyl-carbamoyl)vinylphosphate!; carbamate compoundssuch as BPMC 2-sec-butylphenyl-methylcarbamate!, Benfuracarb ethyl N-2,3-dihydro-2,2-dimethylbenzofuran-7-yloxy-carbonyl(methyl)aminothio!-N-isopropyl-β-alaninate!,Propoxur 2-isopropoxyphenyl N-methylcarbamate!, Carbosulfan2,3-dihydro-2,2-dimethyl-7-benzo b!furanylN-dibutyl-aminothio-N-methylcarbamate!, Carbaril1-naphthyl-N-methylcarbamate!, Methomyl S-methyl-N-(methylcarbamoyl)oxy!thioacetimidate!, Ethiofencarb2-(ethylthiomethyl)-phenylmethylcarbamate!, Aldicarb2-methyl-2-(methylthio)propanaldehyde O-methyl-carbamoyloxime! andOxamyl N,N-dimethyl-2-methylcarbamoyloxyimino-2-(methyl-thio)acetamide!;pyrethroid compounds such as Etofenprox2-(4-ethoxyphenyl)-2-methylpropyl-3-phenoxybenzylether!, Fenvalerate(RS)-α-cyano-3-phenoxybenzyl (RS)-2-(4-chlorophenyl)-3-methylbutyrate!,Esfenvalerate (S)-α-cyano-3-phenoxybenzyl(S)-2-S)-α-cyano-3-phenoxybenzyl2,2,3,3-tetramethylcyclopropanecarboxylate!, Cyper-methrin(RS)-α-cyano-3-phenoxybenzyl(1RS,3RS)-3-(2,2-dichlorovinyl)-2,2-dimethyl-cyclopropanecarboxylate!,Permethrin 3-phenoxybenzyl(1RS,3RS)-(1RS,3RS)-3-(2,2-dichlorovinyl)-2,2-methylcyclopropanecarboxylate!,Cyhalothrin (RS)-α-cyano-3-phenoxybenzyl(Z)-(1RS)-3-(2-chloro-3,3,3-trifluoropropenyl)-2,2-dimethylcyclopropane-carboxylate!,Deltamethrin (S)-α-cyano-m-phenoxybenzyl(1R,3R)-3-(2,2-dibromo-vinyl)-2,2-dimethylcyclopropanecarboxylate! andCycloprothrin (RS)-α-cyano-3-phenoxybenzyl(RS)-2,2-dichloro-1-(4-ethoxyphenyl)cyclopropanecarboxylate!;thiadiazine derivatives such as Buprofezin2-tert-butylimino-3-isopropyl-5-phenyl-1,3,5-thiadiazin-4-one!;nitroimidazolidine derivatives such as Imidacloprid1-(6-chloro-3-pyridyl-methyl)-N-nitroimidazolidin-2-ylidenamine!;Nereistoxin derivatives such as CartapS,S'-(2-dimethylaminotrimethylene)bis(thiocarbamate)!, ThiocyclamN,N-dimethyl-1,2,3-trithian-5-ylamine! and BensultapS,S'-2-dimethylaminotrimethylene di(benzene-thiosulfonate)!; chlorinatedhydrocarbon compounds such as Endosulfan6,7,8,9,10,10-hexachloro-1,5,5a,6,9,9a-hexahydro-6,9-methano-2,4,3-benzodioxathiepinoxide!and γ-BHC 1,2,3,4,5,6-hexachlorocyclohexane!; benzoylphenylureacompounds such as Chlorfluazuron1-(3,5-dichloro-4-(3-chloro-5-trifluoromethylpyridin-2-yloxy)phenyl)-3-(2,6-difluorobenzoyl)urea!,Teflubenzuron1-(3,5-dichloro-2,4-difluorophenyl)-3-(2,6-difluorobenzoyl)urea! andFulphenoxron1-(4-(2-chloro-4-trifluoromethylphenoxy)-2-fluorophenyl)-3-(2,6-difluorobenzoyl)urea!;formamidine derivatives such as Amitraz N,N'(methylimino)dimethylidine!-di-2,4-xylidine! and ChlordimeformN'-(4-chloro-2-methylphenyl)-N,N-dimethylmethanimidamide!.

When used as the active ingredients of harmful-organism controllingagents, the present compounds, although they may be used as such withoutany addition of other ingredients, are usually used as formulations suchas oil sprays, emulsifiable concentrates, wettable powders, flowableconcentrates for water-based suspensions or water-based emulsions;granules, dusts, aerosols, heating fumigants, e.g., fumigants of theself-combustion type, chemical reaction type or porous ceramic platetype; ULV agents or poison baits, by mixing them with solid carriers,liquid carriers, gaseous carriers or baits, and, if necessary, addingsurfactants and other adjuvants for use in formulation.

These formulations contain the present compounds as the activeingredients usually in a proportion of from 0.001% to 95% by weight.

As the solid carrier to be used for formulation, there can be mentioned,for example, fine powder or granules of clay materials (e.g., kaolinclay, diatomaceous earth, synthetic hydrated silicon oxide, bentonite,Fubasami clay, acid clay), various kinds of talc, ceramics and otherinorganic minerals (e.g., sericite, quartz, sulfur, active carbon,calcium carbonate, hydrated silica) and chemical fertilizers (e.g.,ammonium sulfate, ammonium phosphate, ammonium nitrate, urea, ammoniumchloride). As the liquid carrier, there can be mentioned, for example,water, alcohols (e.g., methanol, ethanol), ketones (e.g., acetone,methyl ethyl ketone), aromatic hydrocarbons (e.g., benzene, toluene,xylene, ethylbenzene, methylnaphthalene), aliphatic hydrocarbons (e.g.,hexane, cyclohexane, kerosine, gas oil), esters (e.g., ethyl acetate,butyl acetate), nitriles (e.g., acetonitrile, isobutyronitrile), ethers(e.g., diisopropyl ether, dioxane), acid amides (e.g.,N,N-dimethylformamide, N,N-dimethylacetamide), halogenated hydrocarbons(e.g., dichloromethane, trichloroethane, carbon tetrachloride), dimethylsulfoxide and vegetable oils (e.g., soybean oil, cottonseed oil). As thegaseous carrier or propellant, there can be mentioned, for example, flongas, butane gas, LPG (liquefied petroleum gas), dimethyl ether andcarbon dioxide.

As the surfactant, there can be mentioned, for example, alkyl sulfates,alkyl sulfonates, alkyl arylsulfonates, alkyl aryl ethers and theirpolyoxyethylene derivatives, polyethylene glycol ethers, polyhydricalcohol esters and sugar alcohol derivatives.

As the adjuvant for use in formulation, such as fixing agents ordispersing agents, there can be mentioned, for example, casein, gelatin,polysaccharides (e.g., starch powder, gum arabic, cellulose derivatives,alginic acid), lignin derivatives, bentonite, sugars and syntheticwater-soluble polymers (e.g., polyvinyl alcohol, polyvinyl pyrrolidone,polyacrylic acid). As the stabilizer, there can be mentioned, forexample, PAP (isopropyl acid phosphate), BHT(2,6-di-tert-butyl-4-methylphenol), BHA (mixtures of2-tert-butyl-4-methoxyphenol and 3-tert-butyl-4-methoxyphenol),vegetable oils, mineral oils, surfactants, fatty acids or their esters.

As the base material for fumigants of the self-combustion type, therecan be mentioned, for example, combustion heat-generating agents such asnitrate salts, nitrite salts, guanidine salts, potassium chlorate,nitrocellulose, ethyl cellulose and wood powder; thermolysis stimulatorssuch as alkali metal salts, alkaline earth metal salts, dicromates andcromates; oxygen suppliers such as potassium nitrate; combustion aidssuch as melamine and wheat starch; extending agents such as diatomaceousearth; and binders such as synthetic paste.

As the base material for fumigants of the chemical reaction type, therecan be mentioned, for example, exothermic agents such as sulfides,polysulfides, hydrosulfides and salt hydrates of alkali metals, andcalcium oxide; catalytic agents such as carbonaceous materials, ironcarbide and activated clay; organic foaming agents such asazodi-carbonamide, benzenesulfonyl hydrazine,dinitropentamethylenetetramine, polystyrene and polyurethane; andfillers such as natural fiber chips and synthetic fiber chips.

As the base material for poison baits, there can be mentioned, forexample, bait ingredients such as grain powder, vegetable oils, sugarsand crystalline cellulose; antioxidants such as dibutylhydroxytolueneand nordihydroguaiaretic acid; preservatives such as dehydroacetic acid;feeding-error preventing agents such as red pepper powder; andattractant flavors such as cheese flavor and onion flavor.

The formulations such as flowable concentrates (for water-basedsuspensions or water-based emulsions) are usually obtained by suspending1-75% compound in water containing 0.5-15% dispersing agents, 0.1-10%suspending agents (e.g., protective colloids or thixotropy-impartingcompounds) and 0-1.0% appropriate adjuvants (e.g., defoaming agents,anti-corrosive agents, stabilizing agents, spreading agents, penetrationaids, anti-freezing agents, anti-fungus agents, anti-smoking agents).Various oils in which the present compounds are substantially insolublemay be used instead of water to give oil-based suspensions. As theprotective colloid, there can be mentioned, for example, gelatin,casein, various kinds of gum, cellulose ethers and polyvinyl alcohol. Asthe thixotropy-imparting compound, there can be mentioned, for example,bentonite, aluminum magnesium silicate, xanthane gum and polyacrylicacid.

The formulations thus obtained are used as such or after diluted withwater or the like. They may be used, in admixture or without mixing,with other insecticides, nematocides, acaricides, fungicides,herbicides, plant growth regulators, synergists, fertilizers, soilconditioners, animal feed and the like.

When the present compounds are used as the harmful-organism controllingagents for agriculture, the application amount thereof is usually in therange of 0.001 to 500 g, preferably 0.1 g to 500 g, per 10 ares. Theirformulations such as emulsifiable concentrates, wettable powders andflowable concentrates are usually used after diluted with water to anapplication concentration of 0.0001 to 1000 ppm. Their formulations suchas granules and dusts are used as such without any dilution. When thepresent compounds are used as the harmful-organism controlling agentsfor epidemic prevention, their formulations such as emulsifiableconcentrates, wettable powders and flowable concentrates are usuallyused after diluted with water to an application concentration of 0.0001to 10000 ppm, and their formulations such as oil sprays, aerosols,fumigants, ULV agents and poison baits are used as such.

All of these application amounts and application concentrations may varywith the formulation type, application time, application place,application method, kind of harmful organisms such as noxious insects,noxious mites and ticks, degree of damage and other conditions, and theycan be increased or decreased without limitation to the above range.

EXAMPLES

The present invention will be further illustrated by the followingproduction examples, formulation examples and test examples; however,the present invention is not limited to these examples.

Production Example 1 Production of compound 1 by production process a

To a mixture of 10 ml of anhydrous N,N-dimethylformamide and 72 mg ofsodium hydride (60% oil dispersion) was added dropwise an anhydrousN,N-dimethyl-formamide (5 ml) solution of 300 mg of4-(1-pyrazolyl)methylphenol under stirring over 10 minutes. Afterstirring at room temperature for 1 hour, the mixture was cooled to 5° to10° C., to which an anhydrous N,N-dimethylformamide (5 ml) solution of505 mg of 2-(2-pyridyloxy)ethyl p-toluenesulfonate was added dropwiseover 30 minutes. The mixture was stirred at room temperature overnightand then at 60° to 70° C. for further 2 hours. The reaction mixture waspoured into 50 ml of ice water, which was extracted twice with 30 ml ofethyl acetate. The organic layers were combined, washed with water,dried with anhydrous magnesium sulfate, and concentrated under reducedpressure. The residue was subjected to silica gel column chromatography,which afforded 208 mg of 4-(1-pyrazolyl)methylphenyl2-(2-pyridyloxy)ethyl ether (compound 1). Yield, 41%.

m.p., 82.7° C.

Production Example 2 Production of compound 2 by production process b

To a mixture of 10 ml of anhydrous N,N-dimethylformamide and 96 mg ofsodium hydride (60% oil dispersion) was added dropwise an anhydrousN,N-dimethyl-formamide (5 ml) solution of 500 mg of 2-4-(1-pyrazolyl)methylphenoxy!ethanol (produced in Reference ProductionExample 1 described below) under stirring over 10 minutes. Afterstirring at 60° to 70° C. for 2 hours, the mixture was cooled to 5° to10° C., to which an anhydrous N,N-dimethylformamide (5 ml) solution of288 mg of 2-chloropyrimidine was added dropwise over 30 minutes. Themixture was then stirred at room temperature overnight and then at 60°to 70° C. for further 2 hours. The reaction mixture was poured into 50ml of ice water, which was extracted with twice with 30 ml of toluene.The organic layers were combined, washed with water, dried withanhydrous magnesium sulfate, and concentrated under reduced pressure.The residue was subjected to silica gel column chromatography, whichafforded 339 mg of 4-(1-pyrazolyl)methyl-phenyl 2-(2-pyrimidyloxy)ethylether (compound 2). Yield, 50%.

m.p., 81.7° C.

Production Example 3 Production of compound 3 by production process c

To a mixture of 5 ml of anhydrous N,N-dimethylformamide and 51 mg ofsodium hydride (60% oil dispersion) is added dropwise an anhydrousN,N-dimethylformamide (3 ml) solution of 121 mg of 2-hydroxypyridineunder stirring over 10 minutes. After stirring at room temperature for 1hour, the mixture is cooled to 5° to 10° C., to which an anhydrousN,N-dirmethylformamide (2 ml) solution of 300 mg of 2-4-(2-2H-1,2,3-triazolyl)methylphenoxy!ethyl bromide is added dropwiseover 30 minutes. The mixture is then stirred at room temperatureovernight. The reaction mixture is poured into 50 ml of ice water, whichis extracted with twice with 30 ml of toluene. The organic layers arecombined, washed with water, dried with anhydrous magnesium sulfate, andconcentrated under reduced pressure. The residue is subjected to silicagel column chromatography, which affords4-(2-2H-1,2,3-triazolyl)methylphenyl 2-(2-pyridyloxy)ethyl ether.

Production Example 4 Production of compound 5 by production process b

To a mixture of 10 ml of anhydrous N,N-dimethylformamide and 110 mg ofsodium hydride (60% oil dispersion) was added dropwise an anhydrousdimethylsulfoxide (5 ml) solution of 500 mg of 2-4-(1-pyrazolyl)methylphenoxy!ethanol (produced in Reference ProductionExample 1 described below) under stirring over 10 minutes. Afterstirring at 60° to 70° C. for 2 hours, the mixture was cooled to 5° to10° C., to which an anhydrous N,N-dimethylformamide (5 ml) solution of488 mg of 2-bromothiazole was added dropwise over 10 minutes. Themixture was then stirred at room temperature over-night and then at 60°to 70° C. for further 2 hours. The reaction mixture was poured into 50ml of ice water, which was extracted with twice with 30 ml of toluene.The organic layers were combined, washed with water, dried withanhydrous magnesium sulfate, and concentrated under reduced pressure.The residue was subjected to silica gel column chromatography, whichafforded 280 mg of 4-(1-pyrazolyl)methylphenyl 2-(2-thiazolyl-oxy)ethylether (compound 5). Yield, 41%.

m.p., 65.6° C.

Production Example 5 Production of compound 8 by production process b

To a mixture of 10 ml of anhydrous N,N-dimethylformamide and 24 mg ofsodium hydride (60% oil dispersion) was added dropwise an anhydrousN,N-dimethylformamide (5 ml) solution of 500 mg of 2-2-chloro-4-(1-pyrazolyl)methylphenoxy!-ethanol (produced in ReferenceProduction Example 3 described below) under stirring over 10 minutes.After stirring at 60° to 70° C. for 2 hours, the mixture was cooled to5° to 10° C., to which an anhydrous N,N-dimethylformamide (5 ml)solution of 250 mg of 2-fluoropyridine was added dropwise over 30minutes. The mixture was then stirred at room temperature overnight andthen at 60° to 70° C. for further 2 hours. After completion of thereaction, the reaction mixture was poured into 50 ml of ice water, whichwas extracted with twice with 30 ml of toluene. The organic layers werecombined, washed with water, dried with anhydrous magnesium sulfate, andconcentrated under reduced pressure. The residue was subjected to silicagel column chromatography, which afforded 595 mg of2-chloro-4-(1-pyrazolyl)methylphenyl 2-(2-pyridyloxy)ethyl ether(compound 8). Yield, 91%.

m.p., 82.3° C.

Some typical examples of the present compounds are shown with theircompound numbers and physical properties in Table 3 (by the definitionof each substituent in the compounds of the general formula P-1).

                                      TABLE 3    __________________________________________________________________________    Compounds of the general formula:     ##STR17##    Compound                        Physical    No.   A        R.sup.1                     R.sup.2                        R.sup.3                           X B      properties    __________________________________________________________________________           ##STR18##                   H H  H  O                              ##STR19##                                    m.p. 82.7° C.    2           ##STR20##                   H H  H  O                              ##STR21##                                    m.p. 81.7° C.    3           ##STR22##                   H H  H  O                              ##STR23##                                     m.p. 120.1° C.    4           ##STR24##                   H H  H  O                              ##STR25##                                    m.p. 84.1° C.    5           ##STR26##                   H H  H  O                              ##STR27##                                    m.p. 65.6° C.    6           ##STR28##                   Cl                     H  H  O                              ##STR29##                                    n.sub.D.sup.20.8 1.5878    7           ##STR30##                   Cl                     H  H  O                              ##STR31##                                    n.sub.D.sup.20.8 1.5925    8           ##STR32##                   Cl                     H  H  O                              ##STR33##                                    m.p. 82.3° C.    9           ##STR34##                   H H  CH.sub.3                           O                              ##STR35##                                    n.sub.D.sup.28.6 1.5638    10           ##STR36##                   H CH.sub.3                        H  O                              ##STR37##                                    n.sub.D.sup.28.1 1.5684    __________________________________________________________________________

The following will describe production examples for the startingcompounds used for the production of the present compounds.

REFERENCE PRODUCTION EXAMPLE 1

A mixture of 60 g of 4-(1-pyrazolyl)methylphenol, 54.9 g of ethylchloroacetate, 95.1 g of potassium carbonate, and 500 ml of anhydrousdimethylformamide was heated at 50° C. under stirring for 5 hours,followed by cooling to room temperature. The reaction mixture was pouredinto 1 liter of water, which was extracted twice with 200 ml of ethylacetate. The organic layers were combined, washed with water, saturatedaqueous ammonium chloride solution and then saturated sodium chloridesolution, dried with anhydrous magnesium sulfate, and concentrated underreduced pressure to give crude ethyl 4-(1-pyrazolyl)methylphenoxyacetateas an oil.

To a suspension of 38 g of lithium aluminum hydride in 500 ml ofanhydrous tetrahydrofuran was added dropwise a solution of the abovecrude ethyl 4-(1-pyrazolyl)-methylphenoxyacetate dissolved in 100 ml ofanhydrous tetrahydrofuran at -78° C. under stirring over 30 minutes. Themixture was stirred at the same temperature for 1 hour and then at -20°C. for further 2 hours. The reaction mixture was cooled again to -78°C., to which 38 ml of water, 38 ml of 15% aqueous sodium hydroxidesolution and then 114 ml of water were added dropwise at the sametemperature and subsequently 500 ml of toluene, 500 ml oftetrahydrofuran and then 200 g of anhydrous sodium sulfate were added,and the mixture was stirred at room temperature for 2 hours. Thereaction mixture was filtered through celite, and the filtrate wasconcentrated under reduced pressure. The residue was subjected to silicagel chromatography, which afforded 64.5 g of 2-4-(pyra-zolyl)methylphenoxy!ethanol as white crystals. Yield, 86% (basedupon 4-(1-pyrazolyl)-methylphenol).

m.p., 56° to 58° C.

REFERENCE PRODUCTION EXAMPLE 2 Production of2-chloro-4-(1-pyrazolyl)methylphenol

(1) Production of 2-chloro-4-methylphenyl 2,2-dimethylpropanoate

To a mixture of 100 g of 2-chloro-4-methylphenol, 92.3 g oftriethylamine and 1 liter of anhydrous tetrahydrofuran was addeddropwise 93.0 g of pivaloyl chloride at 5° to 10° C. under stirring over1 hour. Then, after stirring at the same temperature for 3 hours, thereaction mixture was poured into ice water, which was extracted withdiethyl ether. The organic layer was washed with 3% aqueous hydrochloricacid and then water, dried with anhydrous magnesium sulfate, andconcentrated under reduced pressure. The resulting oil was distilledunder reduced pressure, which afforded 155.3 g of2-chloro-4-methylphenyl 2,2-dimethylpropanoate as a colorless clearliquid. Yield, 97.7%.

b.p., 113°-118° C./5 mmHg; n_(D) ²¹.8 1.4949

(2) Production of 4-bromomethyl-2-chlorophenyl 2,2-dimethylpropanoate

To a mixture of 50.0 g of 2-chloro-4-methylphenyl2,2-dimethylpropanoate, 23.8 g of anhydrous sodium carbonate and 500 mlof carbon tetrachloride was added a very small amount of benzoylperoxide and 35.2 g of bromine was added dropwise at 60° C. understirring over 3 hours. While checking the progress of the reaction (thered color of bromine disappeared), a very small amount of benzoylperoxide was added, if necessary, and stirring was continued until thereaction was thoroughly completed.

After completion of the reaction, the reaction mixture was cooled to 10°C., and undissolved matters were removed by filtration under suction,followed concentration under reduced pressure, which afforded 68.7 g of4-bromomethyl 2-chlorophenyl 2,2-di-methylpropanoate as a pale yellowsolid. Apparent yield, 101.7%. This solid was recrystallized from amixed solvent of hexane and toluene to give white crystals.

m.p., 63.3° C.

(3) Production of 2-chloro-4-(1-pyrazolyl)methylphenyl2,2-dimethylpropanoate

A mixture of 15.3 g of pyrazole, 89.9 g of sodium hydride (60% oildispersion) and 200 ml of anhydrous N,N-dimethylformamide was stirred at60° to 70° C. under a nitrogen atmosphere for 2 hours. After theevolution of hydrogen gas ceased, the mixture was cooled to 10° C. Tothis mixture was added dropwise an anhydrous N,N-di-methylformamide (300ml) solution of 68 g of 4-bromomethyl-2-chlorophenyl2,2-di-methylpropanoate at room temperature under stirring over 1 hour,and the mixture was stirred at 80° C. for 1 hour. After cooling, themixture was poured into ice water, which was extracted with ethylacetate. The organic layer was washed with saturated aqueous ammoniumchloride solution and then saturated sodium chloride solution, driedwith anhydrous magnesium sulfate, and concentrated under reducedpressure. The residue was subjected to silica gel column chromatography,which afforded 39.5 g of 2-chloro-4-(1-pyrazolyl)methylphenyl2,2-dimethylpropanoate as a colorless oil. Yield, 60%.

n_(D) ²¹.8 1.5461

(4) Production of 2-chloro-4-(1-pyrazolyl)methylphenol

A mixture of 20.0 g of 2-chloro-4-(1-pyrazolyl)methylphenyl2,2-dimethyl-propanoate, 50 ml of 20% aqueous sodium hydroxide solutionand 300 ml of ethanol was heated at reflux for 5 hours. The reactionmixture was then concentrated under reduced pressure, to which water wasadded, and the mixture was adjusted to pH 6.0 with concentratedhydrochloric acid. This mixture was extracted with ethyl acetate. Theorganic layer was washed with water, dried with anhydrous magnesiumsulfate, and concentrated under reduced pressure. The residue wassubjected to silica gel column chromatography, which afforded 11.5 g of2-chloro-4-(1-pyrazolyl)methylphenol as white crystals. Yield, 80.7%.

m.p., 152.9° C.

REFERENCE PRODUCTION EXAMPLE 3 Production of 2-2-chloro-4-(1-pyrazolyl)methylphenoxy!ethanol

A mixture of 5.0 g of 2-chloro-4-(1-pyrazolyl)methylphenol (produced inReference Production Example 2), 7.6 g of ethyl chloroacetate, 13.2 g ofpotassium carbonate and 100 ml of anhydrous dimethylformamide was heatedat 50° C. under stirring for 5 hours, and then cooled to roomtemperature. The reaction mixture was poured into 500 ml of water, whichwas extracted twice with 50 ml of ethyl acetate. The organic layers werecombined, washed with water, saturated aqueous ammonium chloridesolution and then saturated sodium chloride solution, dried withanhydrous magnesium sulfate, and concentrated under reduced pressure togive crude ethyl 2-chloro-4-(1-pyrazolyl)methylphenoxyacetate as an oil.

To an anhydrous tetrahydrofuran (100 ml) suspension of 1.2 g of lithiumaluminum hydride was added dropwise a solution of the above crude ethyl2-chloro-4-(1-pyrazolyl)methylphenoxyacetate dissolved in 20 ml ofanhydrous tetrahydrofuran at -78° C. under stirring over 30 minutes. Themixture was stirred at the same temperature for 1 hour and at -20° C.for further 2 hours. The reaction mixture was cooled again to -78° C.,to which 1.2 ml of water, 1.2 ml of 15% aqueous sodium hydroxidesolution and then 3.6 ml of water were added dropwise at the sametemperature and subsequently 100 ml of toluene, 100 ml oftetrahydrofuran and then 50 g of anhydrous sodium sulfate were added,and the mixture was stirred at room temperature for 2 hours. Thereaction mixture was filtered through celite, and the filtrate wasconcentrated under reduced pressure. The residue was subjected to silicagel column chromatography, which afforded 4.48 g of 2-2-chloro-4-(pyrazolyl)methylphenoxy!ethanol as white crystals. Yield,74% (based upon 2-chloro-4-(1-pyrazolyl)methylphenol).

m.p., 88.7° C.

REFERENCE PRODUCTION EXAMPLE 4 Production of2-chloro-4-(2-2H-1,2,3-triazolyl)methylphenol

(1) Production of 2-chloro-4-(2-2H-1,2,3-triazolyl)methylphenyl2,2-di-methylpropanoate

A mixture of 2.26 g of 2H-1,2,3-triazole, 1.31 g of sodium hydride (60%oil dispersion) and 100 ml of anhydrous N,N-dimethylformamide wasstirred at 60° to 70° C. under a nitrogen atmosphere for 2 hours. Afterthe evolution of hydrogen gas ceased, the mixture was cooled to 10° C.To this mixture was added dropwise an anhydrous N,N-di-methylformamide(150 ml) solution of 10 g of 4-bromomethyl-2-chlorophenyl2,2-di-methylpropanoate at room temperature under stirring over 1 hour,and the mixture was stirred at 80° C. for 1 hour. After cooling, thereaction mixture was poured into ice water, which was extracted withethyl acetate. The organic layer was washed with saturated aqueousammonium chloride solution and then saturated sodium chloride solution,dried with anhydrous magnesium sulfate, and concentrated under reducedpressure. The residue was subjected to silica gel column chromatography,which afforded 2-chloro-4-(2-2H-1,2,3-triazolyl)methylphenyl2,2-dimethylpropanoate.

(2) Production of 2-chloro-4-(2-2H-1,2,3-triazolyl)methylphenol

A mixture of 3 g of 2-chloro-4-(2-2H-1,2,3-triazolyl)methylphenyl2,2-di-methylpropanoate, 10 ml of 20% aqueous sodium hydroxide solutionand 60 ml of ethanol was heated at reflux for 5 hours. The reactionmixture was then concentrated under reduced pressure, to which water wasadded, and the mixture was adjusted to pH 6.0 with concentratedhydrochloric acid. This mixture was extracted with ethyl acetate. Theorganic layer was washed with water, dried with anhydrous magnesiumsulfate, and concentrated under reduced pressure. The residue wassubjected to silica gel column chromatography, which afforded2-chloro-4-(2-2H-1,2,3-triazolylmethyl)phenol.

REFERENCE PRODUCTION EXAMPLE 5 Production of2-chloro-4-(2-pyridon-1-yl)methylphenol

(1) Production of 2-chloro-4-(2-pyridon-1-yl)methylphenyl2,2-dimethyl-propanoate

A mixture of 3.11 g of 2-pyridone, 1.31 g of sodium hydride (60% oildispersion) and 100 ml of anhydrous N,N-dimethylformamide was stirred at60° to 70° C. under a nitrogen atmosphere for 2 hours. After theevolution of hydrogen gas ceased, the mixture was cooled to 10° C. Tothis mixture was added dropwise an anhydrous N,N-di-methylformamide (150ml) solution of 10 g of 4-bromomethyl-2-chlorophenyl2,2-di-methylpropanoate at room temperature under stirring over 1 hour,and the mixture was stirred at 80° C. for 1 hour. After cooling, themixture was poured into ice water, which was extracted with ethylacetate. The organic layer was washed with saturated aqueous ammoniumchloride solution and then saturated sodium chloride solution, driedwith anhydrous magnesium sulfate, and concentrated reduced pressure. Theresidue was subjected to silica gel column chromatography, whichafforded 7.60 g of 2-chloro-4-(2-pyridon-1-yl)methylphenyl2,2-dimethylpropanoate as white crystals. Yield, 73%.

m.p., 145.2° C.

(2) Production of 2-chloro-4-(2-pyridon-1-yl)methylphenol

A mixture of 7.6 g of 2-chloro-4-(2-pyridon-1-yl)methylphenyl2,2-dimethyl-propanoate, 19 ml of 20% aqueous sodium hydroxide solutionand 200 ml of ethanol was heated at reflux for 5 hours. The reactionmixture was then concentrated under reduced pressure, to which water wasadded, and the mixture was adjusted to pH 6.0 with concentratedhydrochloric acid. This mixture was extracted with ethyl acetate. Theorganic layer was washed with water, dried with anhydrous magnesiumsulfate, and concentrated under reduced pressure. The residue wassubjected to silica gel column chromatography, which afforded 3.98 g of2-chloro-4-(2-pyridon-1-yl)methylphenol as white crystals. Yield, 71%.

m.p., 193.5° C.

REFERENCE PRODUCTION EXAMPLE 6 Production of 2-4-(1-pyrazolyl)methylphenoxy!ethyl bromide

To a mixture of 15 g of 4-(1-pyrazolyl)methylphenol, 32.4 g of1,2-dibromo-ethane and 150 ml of water was added dropwise 30 ml of anaqueous solution of 4.1 g of sodium hydroxide while stirring underheating at reflux over 2 hours. Then, after heating at reflux understirring for further 30 minutes, the reaction mixture was poured into200 ml of ice water, which was extracted twice with 100 ml of diethylether. The organic layers were combined, washed with 5N aqueous sodiumhydroxide solution, water and then saturated sodium chloride solution,dried with anhydrous magnesium sulfate, and concentrated under reducedpressure. The residue was subjected to silica gel column chromatography,which afforded 11.44 g of 2- 4-(1-pyrazolyl)methylphenoxy!ethyl bromideas white crystals. Yield, 47%.

m.p. 63°-65° C.

The following will describe formulation examples for theharmful-organism controlling agents containing the present compounds asthe active ingredients, in which "parts" are by weight and the presentcompounds are designated by their compound numbers as shown in Table 3.

Formulation Example 1 Emulsifiable concentrates

Ten parts of each of the present compounds 1 to 10 is dissolved in 35parts of xylene and 35 parts of dimethylformamide, to which 14 parts ofpolyoxyethylene styryl phenyl ether and 6 parts of calciumdodecylbenzenesulfonate are added, and the mixture is well stirred togive a 10% emulsifiable concentrate of each compound.

Formulation Example 2 Wettable powders

Twenty parts of each of the present compounds 1 to 10 is added to amixture of 4 parts of sodium lauryl sulfate, 2 parts of calcium ligninsulfonate, 20 parts of synthetic hydrated silicon oxide fine powder and54 parts of diatomaceous earth, and the mixture is stirred with a juicemixer to give a 20% wettable powder of each compound.

Formulation Example 3 Granules

To 5 parts of each of the present compounds 1 to 10 are added 5 parts ofsynthetic hydrated silicon oxide fine powder, 5 parts of sodiumdodecylbenzenesulfonate, 30 parts of bentonite and 55 parts of clay, andthe mixture is well stirred. A suitable amount of water is then added tothis mixture, which is further stirred, granulated with a granulator,and air-dried to give a 5% granule of each compound.

Formulation Example 4 Dusts

To 2 parts of each of the present compounds 1 to 10 is added 5 parts ofpolypropylene glycol, and the mixture is heated over the melting pointfor dissolution, which is then absorbed in 93 parts of granular calcineddiatomaceous earth, which has been warmed, to give a 2% granule of eachcompound.

Formulation Example 5 Dusts

One part of each of the present compounds 1 to 10 is dissolved in asuitable amount of acetone, to which 5 parts of synthetic hydratedsilicon oxide fine powder, 0.3 part of PAP and 93.7 parts of clay areadded, and the mixture is stirred with a juice mixer. The removal ofacetone by evaporation gives a 1% dust of each compound.

Formulation Example 6 Water-based suspension

Twenty parts of each of the present compounds 1 to 10 and 1.5 parts ofsorbitan trioleate are mixed with 28.5 parts of an aqueous solutioncontaining 2 parts of polyvinyl alcohol, and the mixture is pulverizedinto fine particles (particle size, not more than 3 μm) with a sandgrinder, to which 40 parts of an aqueous solution containing 0.05 partof xanthane gum and 0.1 part of aluminum magnesium silicate is added andthen 10 parts of propylene glycol is added. The mixture is stirred togive a 20% water-based suspension of each compound.

Formulation Example 7 Oil sprays

First, 0.1 part of each of the present compounds 1 to 10 is dissolved in5 parts of xylene and 5 parts of trichloroethane. The solution is thenmixed with 89.9 parts of deodorized kerosine to give a 0.1% oil spray ofeach compound.

Formulation Example 8 Oil-based aerosols

First, 0.1 part of each of the present compounds 1 to 10, 0.2 part oftetramethrin, 0.1 part of d-phenothrin, 10 parts of trichloroethane and59.6 parts of deodorized kerosine are mixed for dissolution. Thesolution is put in an aerosol vessel, which is then equipped with avalve. Through the said valve, 30 parts of a propellant (liquefiedpetroleum gas) is charged under increased pressure to give an oil-basedaerosol of each compound.

Formulation Example 9 Water-based aerosols

First, 0.2 part of each of the present compounds 1 to 10, 0.2 part ofd-allethrin, 0.2 part of d-phenothrin, 5 parts of xylene, 3.4 parts ofdeodorized kerosine and 1 part of an emulsifier ATMOS 300 (registeredtrade name by Atlas Chemical Co.)! are mixed for dissolution. Themixture, together with 50 parts of pure water, is put in an aerosolvessel, which is then equipped with a valve. Through the said valve, 40parts of a propellant (liquefied petroleum gas) is charged underincreased pressure to give a water-based aerosol of each compound.

Formulation Example 10 Mosquito-coils

To 0.3 g of each of the present compounds 1 to 10 is added 0.3 g ofd-allethrin, and the mixture is dissolved in 20 ml of acetone. Thesolution is uniformly mixed with 99.4 g of a carrier for mosquito-coils(prepared by mixing Tabu powder, pyrethrum marc powder and wood flour atthe ratio of 4:3:3) under stirring, to which 120 ml of water was added.The mixture is well kneaded, molded, and dried to give a mosquito-coilof each compound.

Formulation Example 11 Electric mosquito-mats

To 0.4 g of each of the present compounds 1 to 10, 0.4 g of d-allethrinand 0.4 g of pipenyl butoxide is added acetone for dissolution, so thatthe total volume comes to 10 ml. This solution in 0.5 ml is uniformlyabsorbed in a substrate forelectric mosquito-mats (prepared by pressinga fibrillated mixture of cotton linter and pulp into a sheet), which is2.5 cm×1.5 cm and 0.3 cm thick, to give an electric mosquito-mat of eachcompound.

Formulation Example 12 Heating smoke formulations

First, 100 mg of each of the present compounds 1 to 10 is dissolved in asuitable amount of acetone, and the solution is then absorbed in aporous ceramic plate of 4.0 cm×4.0 cm and 1.2 cm thick to give a heatingfumigant of each compound.

Formulation Example 13 Poison baits

First, 10 mg of each of the present compounds 1 to 10 is dissolved in0.5 ml of acetone, and this solution is added to 5 g of solid baitpowder for animals (Breeding Solid Feed Powder CE-2, trade name by JapanClea Co., Ltd.), which is uniformly mixed. Then, the removal of acetoneby air drying gives a 0.5% poison bait of each compound.

The following test examples will demonstrate that the present compoundsare useful as the active ingredients of harmful-organism controllingagents, in which the present compounds are designated by their compoundnumbers as shown in Table 3.

Test Example 1 Insecticidal test against common mosquito

An emulsifiable concentrate of the test compound obtained according toFormulation Example 1 was diluted with water, and this dilution in 0.7ml was added to 100 ml of ion-exchanged water to a prescribedconcentration. Twenty last instar larvae of common mosiquito (Culexpipiens pallens) were set free therein, and bred while giving bait for 8days. The emergence inhibitory rate was determined by the followingequation 1. The results are shown in Table 4.

                  TABLE 4    ______________________________________     ##STR38##                      1!                  Application                             Emergence                  concentration                             inhibitory rate    Test compound (ppm)      (%)    ______________________________________    1             3.5        100    1             0.1        100    2             3.5        100    3             3.5        100    4             3.5        100    4             0.1        100    ______________________________________

Test Example 2 Insecticidal test against cotton aphid

An emulsifiable concentrate of the test compound obtained according toFormulation Example 1 was diluted with water to a prescribedconcentration, and the dilution was poured upon the parts near the rootsof cucumbers cultivated in polyethylene cups for flooding at a rate of10 cc/1 pot. After 3 days from the treatment, five adults of cottonaphid (Aphis glossypii) were freely bred on the main leaves. After 14days from the free breeding, the control value was determined by thefollowing equation 2. The results are shown in Table 5. ##EQU1## whereC_(b) is the number of insects before the treatment in the untreatedgroup; C_(ai), the number of insects during the observation in theuntreated group; T_(b), the number of insects before the treatment inthe experimental group; and T_(ai), the number of insects during theobservation in the experimental group.

                  TABLE 5    ______________________________________                  Application                  concentration                             Control value    Test compound (ppm)      (%)    ______________________________________    1             500        82    2             500        96    5             500        100    6             500        90    8             500        79    ______________________________________

Industrial Applicability

According to the present invention, there are provided novel ethercompounds having excellent controlling effects against harmfulorganisms. These ether compounds are useful as the active ingredients ofharmful-organism controlling agents.

We claim:
 1. An ether compound of the formula: ##STR39## wherein R¹ is hydrogen or chlorine; R² and R³ are independently hydrogen or methyl;A is a group of the formula: ##STR40## wherein R⁴ is hydrogen, chlorine or methyl; and R⁵ and R⁶ are independently hydrogen or chlorine; B is a group of the general formula: ##STR41## wherein R⁷ and R⁸ are independently hydrogen or fluorine; and X is oxygen or sulfur.
 2. An ether compound according to claim 1, wherein A is a group of the formula: ##STR42## wherein R⁴ is as defined above.
 3. An ether compound according to claim 2, wherein R⁴ is hydrogen.
 4. An ether compound according to claim 1, wherein R¹ is hydrogen.
 5. 4-(1-Pyrazolyl)methylphenyl 2-(2-pyridyloxy)ethyl ether.
 6. 4-(1-Pyrazolyl)methylphenyl 2-(thiazolyloxy)ethyl ether.
 7. An insecticidal and/or acaricidal agent characterized by comprising an effective amount of an ether compound according to claim 1 as an active ingredient.
 8. An ether compound according to claim 1, wherein A is a group of the formula: ##STR43##
 9. An ether compound according to claim 1, wherein A is a group of the formula: ##STR44## wherein R⁵ and R⁶ are as defined above.
 10. An insecticidal and/or acaricidal agent characterized by comprising an effective amount of an ether compound according to claim 1 as an active ingredient, and a carrier. 